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WO2001004164A2 - Hydrogenation de polymeres insatures a l'aide de diolefine bivalente contenant des catalyseurs metalliques biscyclopentadienyl du groupe iv - Google Patents

Hydrogenation de polymeres insatures a l'aide de diolefine bivalente contenant des catalyseurs metalliques biscyclopentadienyl du groupe iv Download PDF

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WO2001004164A2
WO2001004164A2 PCT/US2000/017163 US0017163W WO0104164A2 WO 2001004164 A2 WO2001004164 A2 WO 2001004164A2 US 0017163 W US0017163 W US 0017163W WO 0104164 A2 WO0104164 A2 WO 0104164A2
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zirconium
cyclopentadienyl
butadiene
trans
bis
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WO2001004164A3 (fr
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David D. Devore
Stephen F. Hahn
James C. Stevens
Francis J. Timmers
David R. Wilson
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Dow Chemical Co
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Dow Chemical Co
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Priority to EP00941639A priority patent/EP1257587B1/fr
Publication of WO2001004164A2 publication Critical patent/WO2001004164A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation

Definitions

  • This invention relates to a process for hydrogenating olefinically unsaturated polymers.
  • R' is hydrogen or an organic radical.
  • polymers of conjugated dienes such as poly (butadiene) , which contain olefinic unsaturation sites either in the polymer chain itself or pendant thereto. For various reasons, it is sometimes desired to eliminate this unsaturation.
  • the olefinic unsaturation is subject to attack by oxidants, heat, radiation or a combination thereof. This causes the polymer to perform poorly in applications where it is exposed to such conditions.
  • Heterogeneous catalysts are often lower in activity than homogeneous catalysts and also often require higher temperature and pressure conditions in order to achieve acceptable reaction rates. The higher temperatures increase energy consumption, thus cost, and can cause the polymer to decompose or the reaction system to gel . Furthermore, a larger amount of heterogeneous catalyst is usually needed on a weight basis, particularly when a high molecular weight polymer is hydrogenated. Also, heterogeneous catalysts are often not selective and can sometimes catalyze hydrogenation of other portions of the polymer, particularly aromatic rings, which may be undesirable for some applications.
  • a catalyst which provides reasonably facile hydrogenation under mild or moderate conditions, leaves colorless residues and which avoids known environmental or disposal problems. It is further desirable that the catalyst provides for selective hydrogenation. This is particularly the case where the polymer being hydrogenated contains, in addition to the olefinic unsaturation, other sites that are also subject to hydrogenation or reduction.
  • a prominent example of such a polymer is a copolymer of a diene, such as butadiene, and a vinyl aromatic, such as styrene. Often it is desired to remove the residual unsaturation that is inherent in diene polymers without hydrogenating the rings of the vinyl aromatic monomers.
  • the catalyst desirably is highly selective for the olefinic unsaturation, yet provides for facile reaction. Further, it would be desirable to hydrogenate a polymer, copolymer or mixture thereof having olefinic unsaturation while minimizing cleavage or degradation of the polymer backbone, thus retaining polymer molecular weight through the hydrogenation process.
  • This invention is a process for selectively hydrogenating at least one polymer or copolymer or mixture thereof containing olefinic unsaturation.
  • the process comprises reacting or contacting the polymer, copolymer or mixture thereof with a hydrogenating agent in the presence of a catalytic amount of a divalent Group IV metal compound, which is represented by the structure:
  • M is titanium, zirconium or hafnium
  • Cp and Cp ' are each substituted or unsubstituted cyclopentadienyl ligands, which are optionally the same or different from each other and optionally Cp and Cp' include substituents which form a bridging group connecting Cp and Cp '
  • D represents a conjugated, neutral diene, which is coordinated via ⁇ complexation to the M atom.
  • the process is particularly suited for hydrogenating a copolymer of at least one conjugated diene and at least one vinyl aromatic monomer.
  • cleavage and degradation of the polymer backbone is minimized relative to cleavage or degradation observed using other hydrogenation catalysts as demonstrated by retention of polymer molecular weight through the hydrogenation process.
  • a polymer, copolymer or mixture thereof containing olefinic unsaturation is hydrogenated m the presence of a divalent titanium, zirconium or hafnium compound, which is represented by the structure:
  • the Cp and Cp ' groups are each cyclopentadienyl ligands having the general structures: C 5 R 5 and C 5 R' 5 , respectively, wherein the R and R' groups are independently hydrogen, hydrocarbyl, silyl, siloxy, germyl, ammo, hydrocarbyloxy, dihydrocarbylboryl, cyano or halogen.
  • R or R' is hydrocarbyl, silyl or germyl, it optionally contains inert substituents, in the sense that the substituents do not undesirably interfere with or react during the hydrogenation reaction.
  • the R groups are optionally the same or different from each other, as are optionally the R' groups.
  • R groups are optionally the same as or different than the R' groups.
  • R groups and one or more R' groups optionally together form a divalent radical which links the Cp and Cp ' groups together.
  • the R and R' groups preferably form a linking diradical having the structure -(ER" 2 ) X - wherein each E is independently a carbon, silicon or germanium atom, R" is independently in each occurrence hydrogen, silyl, hydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, siloxy, or two R" groups together form a ring system including the E atom or atoms to which they are attached.
  • R" optionally has up to 30 carbon, silicon, nitrogen or oxygen atoms.
  • R" is preferably hydrogen, methyl, ethyl, methoxy, benzyl, tert-butyl or phenyl .
  • "x" is a number from 1 to 8.
  • the R and R' groups optionally preferably form a linking diradical having the structure -(E'R") X - wherein each E' is independently a boron or aluminum atom and R" and x have the meanings above.
  • E' is boron and R" is hydrocarbylamino, more preferably dimethylamino or diisopropylamino.
  • the R and R' groups which are not part of the linking diradical, are selected from the group consisting of hydrogen, methyl, ethyl, the various propyl, butyl, pentyl and hexyl isomers, cyclopentyl, cyclohexyl, norbornyl, phenyl, benzyl, trimethyl silyl, methoxy, ethoxy, trimethylsiloxy, dimethylamino, pyrrolidino, piperidino and dimethylboryl .
  • Cp and Cp ' groups wherein adjacent R or R' groups are linked together to form a ring fused to the cyclopentadiene ring as, for example, indenyl, 2-methyl-4-phenylindenyl, 2-methyl-4- (ortho-methyl- phenyl) indenyl, 2-methyl-4- (3, 5-dimethyl-phenyl ) indenyl, 2-methyl-4-naphthylindenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl groups.
  • R and R' groups which together form a divalent radical linking the Cp and Cp ' groups, such as methylene, 1, 2-ethanediyl, 2, 2-propanediyl and dimethylsilanediyl linking groups, are also preferred.
  • cyclopentadienyl groups include cyclopentadienyl , methylcyclopentadienyl , trimethylsilylcyclopentadienyl, t-butylcyclopentadienyl, tetramethylcyclopentadienyl , pentamethylcyclopentadienyl , indenyl, 2-methyl-4-phenylindenyl, 2-methyl-4- (ortho-methyl- phenyl) indenyl, fluorenyl, dimethylaminoindenyl and pyrrolidinoindenyl groups.
  • M is preferably titanium or zirconium.
  • the D group is a conjugated, neutral diene which is coordinated via ⁇ -complexation through the diene double bonds, and not through ⁇ -bonds which form a metallocycle ( ⁇ -bound diene) . It preferably contains from 5 to 30 atoms not including hydrogen.
  • the diene is substituted in either or both of the 1 and 4 positions (the 1 and 4 positions indicating the terminal carbons on the conjugated diene group) .
  • the diene is 1- or 1,4- substituted to form more stable ⁇ -complexes rather than ⁇ -bonds.
  • ⁇ -complex it is meant that both the donation and back acceptance of electron density by the diene ligand are accomplished using ligand ⁇ -orbitals ( ⁇ -bound diene) .
  • a convenient method of determining the existence of a ⁇ - or ⁇ -complex in conjugated diene-containing metal complexes is by measuring metal-carbon atomic spacings for the four carbons which constitute the conjugated diene group, using common X-ray crystal analysis techniques. Measurements of atomic spacings between the metal and Cl, C2, C3, and C4 (M-Cl, M-C2, M-C3, M-C4, respectively) (where Cl and C4 are the terminal carbons of the 4 carbon conjugated diene group and C2 and C3 are the internal carbons of the 4 carbon conjugated diene group) are made. If the difference between these bond distances, ⁇ d, using the following formula:
  • Another method of distinguishing a ⁇ -complex from a ⁇ -bound diene is by using nuclear magnetic resonance spectroscopy techniques, as described in Erker, et al . , supra , C. Kruger, et al . Organometallic, 4, 215-223, (1985), and Yasuda et al . , Organometallics , 1, 388 (1982) .
  • the teachings of the foregoing references relating to distinguishing ⁇ -bound from ⁇ -bound complexes represent the skill in the art.
  • Preferred D groups include, for example, ⁇ 4 -l-4- diphenyl-1, 3-butadiene; ⁇ 4 -2, 4-hexadiene; ⁇ 4 -3-methyl- 1, 3-pentadiene; ⁇ 4 -l, 3-pentadiene; ⁇ 4 -l, 4-bis (tri- methylsilyl) -1, 3-butadiene; ⁇ -l-phenyl-l, 3-pentadiene; ⁇ 4 -l, 4-tolyl-l, 3-butadiene; and ⁇ 4 -l, 4-dibenzyl-l, 3-butadiene .
  • Any of the ligands are optionally bound to the Group IV metal in the cis or trans form.
  • titanium or zirconium complexes when prepared, a mixture of the ⁇ -complexed and ⁇ - complexed diene compounds is often obtained. It is within the scope of this invention to employ a titanium, hafnium or zirconium complex as described in combination with the corresponding ⁇ -complex as an impurity. Alternatively, the ⁇ -complex is optionally separated out using techniques such as disclosed in Yasuda and Erker. It is also understood that, in the present invention, the bridged metal complexes are optionally employed as mixtures of the racemic and meso isomers or alternatively the meso isomer is optionally separated using standard recrystallization techniques.
  • a preferred method for preparing the racemic isomers is to synthesize this isomer in high or complete isomeric purity using Zr(II) diene complexes such as Zr (PR 3 ) 2 C1 2 ( ⁇ 4 -l-4-diphenyl-l, 3-butadiene) as template reagents for the stereoselective complexation of the bridged bis-indenyl or bis-cyclopentadienyl reagents.
  • Zr(II) diene complexes such as Zr (PR 3 ) 2 C1 2 ( ⁇ 4 -l-4-diphenyl-l, 3-butadiene) as template reagents for the stereoselective complexation of the bridged bis-indenyl or bis-cyclopentadienyl reagents.
  • Examples of the above metal complexes, wherein the metal is zirconium include: bis ( ⁇ 5 -cyclopentadienyl) zirconium s-trans ( ⁇ 4 -l, 4-trans, trans-diphenyll, 3-butadiene) , bis (- ⁇ 5 -cyclopentadienyl) zirconium ⁇ -l, 4-ditolyl-l, 3-butadiene, bis ( ⁇ 5 -cyclopentadienyl) zirconium (4-1-4-benzyl-l , 3-butadiene, bis ( ⁇ 5 -cyclopentadienyl) zirconium ⁇ 4 -2, 4-hexadiene, bis ( ⁇ 5 -cyclopentadienyl) zirconium ⁇ -3-methyl-l, 3-pentadiene, bis ( ⁇ 5 -cyclopentadienyl) zirconium ⁇ 4 -l-phenyl-l , 3-pentadiene, bis (p
  • Exemplary bridged cyclopentadienyl complexes include: dimethylsilanediyl-bis ( (2-methyl-4-phenyl ) -1-indenyl) zirconium s-trans ( ⁇ 4 -l, 4-trans-trans-diphenyl-l, 3-butadiene) , dimethylsilanediyl-bis ( (2-methyl-4- (1- naphthyl) ) -1-indenyl) zirconium s-trans ( ⁇ -l, 4-trans- trans-diphenyl-l, 3-butadiene) , 1, 2-ethanediyl-bis (2- methyl-4- (1-phenyl) -1-indenyl) zirconium s-trans ( ⁇ 4 -l, 4- trans-trans-diphenyl-1, 3-butadiene) , 1, 2-ethanediyl- bis (2-methyl-4- (1-naphthyl) -1-indenyl) zircon
  • the complexes useful in the present invention can be prepared by combining a diene compound, corresponding to the group D in the resulting complex, with a metal complex of the formula CpCp'ML a , wherein Cp, Cp ' and M are as defined before, L is a leaving group, and a is 1 or 2.
  • Leaving groups L include neutral Lewis bases, such as amines, phosphines, alkenes and carbon monoxide, and radicals, such as hydrocarbyl, hydrocarbyloxy, siloxy, amide or halogen.
  • Preferred L groups are timethylamine, trimethylphosphine, triethylphosphine, carbon monoxide, ethylene, propylene, ethyl, benzyl, butyl, phenyl, methoxy, phenoxy, dimethylamido, chloro, bromo and iodo.
  • the valence of M is 2, 3 or .
  • the replacement of the leaving group (s) with the diene is optionally carried out at room temperature or at elevated temperature.
  • the leaving groups L are neutral Lewis bases or hydrocarbyl groups, this replacement is optionally expedited by heating the mixture of the diene and starting complex, such as in refluxing toluene.
  • the starting complex is optionally contacted with a reducing agent.
  • the contacting with a reducing agent can be done simultaneously with the contacting of the diene with the starting metal complex, or afterward.
  • the contacting of the starting complex with the diene, reducing agent or a combination of diene and reducing agent is optionally carried out in a noninterfering solvent, if desired, and over a temperature range from -100°C to 300°C, preferably from -78°C to 130°C, more preferably from -10°C to 120°C.
  • noninterfereing solvent is meant a solvent for reactants that does not undesirably interfere with the formation of the metal complex.
  • some halogenated solvents under certain reaction conditions, facilitate oxidation of the metal to a higher oxidation state than is desired.
  • Some protic sovents like water, methanol, acetic acid, certain ketones, aldehydes, nitriles and the like are capable under some reaction conditions of reacting to result in oxidized titanium metal.
  • some solvents are capable of complexing the metal preferentially as compared with the diene or desired ligand. Under reaction conditions where interfering reactions are observed to an undesirable extent, the solvents capable of entering into the reactions are preferably avoided.
  • reducing agent a metal or compound which, under reducing conditions can cause the transition metal to be reduced from the +4 or +3 formal oxidation state to the +2 formal oxidation state.
  • the same procedure is employed for the preparation of the diene complexes where M is in the +2 formal oxidation state or in the +4 formal oxidation state, the nature of formal oxidation state of M in the complex being formed being primarily determined by the diene employed.
  • useful metal reducing agents are alkali metals, alkaline earth metals, aluminum, zinc and alloys of alkali metals or alkaline earth metals, such as sodium/mercury amalgam and sodium/potassium alloy.
  • useful reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, aluminum t ⁇ alkyls and G ⁇ gnard reagents.
  • Most preferred reducing agents are the alkali metals or alkaline earth metals, C ⁇ _ 6 alkyl lithium, t ⁇ C ⁇ _ 6 alkyl aluminum and G ⁇ gnard reagents, especially lithium, n-butyl lithium and t ⁇ ethyl aluminum.
  • the use of a C ⁇ _ 6 alkyl lithium or triethylalummum reducing agent is especially preferred.
  • Highly preferred diene compounds are 1 , 3-pentadiene;
  • Useful reaction media for the formation of the complexes are aliphatic and aromatic hydrocarbons and halohydrocarbons, ethers, and cyclic ethers. Examples include straight and branched-cham hydrocarbons, such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds, such as benzene, toluene, xylene, C ⁇ _ 4 dialkyl ethers, C ⁇ - 4 dialkyl ether derivatives of (poly) alkylene glycols, and tetrahydrofuran. Mixtures of solvents from the foregoing list of solvents are also useful.
  • the recovery procedure involves separation of the resulting byproducts and devolatilization of the reaction medium. Extraction into a secondary solvent is optionally employed, if desired. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation technique is optionally employed.
  • (L-A-L)M'D' (Formula 2) or a Lewis base adduct thereof comprises, contacting in any order a Group 4 metal complex corresponding to the formula M'X 2 D' or a Lewis base adduct thereof, and a compound of the formula: (L-A-L)M" n ; wherein:
  • M' is titanium, zirconium or hafnium in the +2 formal oxidation state corresponding to a preferred M in Formula 1 : CpCp'M»D) ;
  • M" is hydrogen or a Group 1 metal cation, a Group 2 metal or zinc dication, a magnesium- or zinc monohalide cation, a tri (C ⁇ o hydrocarbyl) silyl group, a tri (C,_ 20 hydrocarbyl ) tin group, a mono (C ⁇ - 2 o hydrocarbyl) aluminum group; a di (C 1-20 hydrocarbyl ) aluminum group; or a mono (C 1-2 o hydrocarbyl) zinc group, with the proviso that M" is labile under the reaction conditions;
  • L is an anionic ligand group (each L independently corresponding to one of Cp or Cp ' in Formula 1 except that in Formula 1, Cp and Cp ' optionally have substituents that correspond to A)) bonded to A, except in the formula (L-A-L)M" n when M" is hydrogen or silyl, L is a neutral ligand group bonded to A, said L group containing up to 50 atoms other than hydrogen;
  • A is a divalent bridging group joining two L groups
  • D' is a neutral, substituted derivative of 1,3- butadiene, substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, at least one of said substituents being located at the 1- or 4-position, said D' having from 5 up to 40 atoms other than hydrogen (D' corresponding to a preferred D in Formula 1) ;
  • X independently each occurrence is a monovalent anionic leaving group of up to 50 atoms other than hydrogen, and optionally, two X groups are joined together thereby forming a divalent anionic leaving group; and n is 1 or 2, and recovering the resulting product.
  • this process is referred to herein as using diene complexes as template reagents for the stereoselective complexation of the bridged bis-cyclopentadienyl or bis-indenyl reagents.
  • the foregoing process results in the production of primarily the racemic isomer of the metal complex (L-A- L)M'D', or its Lewis base adduct.
  • products containing greater than 60 mole percent, more preferably greater than 70 mole percent of the racemic isomer are formed without use of purification or isomer separation techniques.
  • the process is capable of producing the racemic isomer in essentially pure form and in high yields. This result is believed to be due to the unique chemical properties of the starting reactant.
  • the Group 4 metal complex corresponding to the formula
  • M'X 2 D' or a Lewis base adduct thereof is optionally prepared by a process comprising contacting in any order, in an inert diluent, and optionally in the presence of a Lewis base, a Group 4 metal complex corresponding to the formula, M1X 4 , or M1X 4 (L') k with a compound corresponding to the formula D''M'" n '; wherein,
  • Ml is titanium, zirconium or hafnium in the +4 formal oxidation state
  • X independently each occurrence is a monovalent anionic leaving group of up to 50 atoms other than hydrogen, and optionally, two X groups are joined together thereby forming a divalent anionic leaving group;
  • L' is a Lewis base; k is a number from 0 to 3; D 1 ' is a divalent derivative of a substituted 1,3- butadiene which is substituted with one or more hydrocarbyl groups, silyl groups, hydrocarbylsilyl groups, silylhydrocarbyl groups, or mixtures thereof, at least one of said substituents being located at the 1- or 4-pos ⁇ t on, and said D'' having from 5 up to 40 atoms other than hydrogen;
  • M' is a Group 1 metal cation, a Group 2 metal or zinc dication, a magnesium- or zinc monohalide cation, a mono(C 120 hydrocarbyl) aluminum group; a di ( 20 hydrocarbyl) aluminum group; or a mono(C ⁇ 20 hydrocarbyl) zinc group; and
  • the Group 4 metal complex corresponding to the formula M'X 2 D' or a Lewis base adduct thereof is prepared by a process comprising contacting in any order, n an inert diluent, and optionally in the presence of a Lewis base, a Group 4 metal complex corresponding to the formula, M1X, or M1X 4 (L') k with a reducing agent to prepare a dimeric compound corresponding to the formula:
  • M' is titanium, zirconium or hafnium in the +2 formal oxidation state
  • Ml is titanium, zirconium or hafnium m the +4 formal oxidation state
  • M2 is titanium, zirconium or hafnium m the +3 formal oxidation state
  • X independently each occurrence is a monovalent anionic leaving group of up to 50 atoms other than hydrogen, and optionally, two X groups (excluding bridging anion X groups) are joined together thereby forming a divalent anionic leaving group L' is a Lewis base, and k is a number from 0 to 3.
  • the reducing agent in the foregoing process is an alkali metal or alkali metal alkyl, most preferably lithium or lithium alkyl
  • the inert diluent is a hydrocarbon liquid, most preferably an aliphatic or aromatic hydrocarbon.
  • the process is an integrated processes incorporating the foregoing individual processes in varying combination.
  • Preferred metals, M', Ml and M 2 are titanium and zirconium.
  • Preferred M" groups are Li + , K + , Na + , and Grignard cations.
  • Preferred M'" groups are also Li + , K + , Na + , and Grignard cations .
  • L groups are the Cp and Cp ' groups described for Formula 1, except that Cp and Cp ' include as substituents A, which is separately defined for Formula 2.
  • Preferred L groups are cyclic (including polycyclic) hydrocarbyl groups or heteroatom containing hydrocarbyl groups, or such groups further substituted with one or more substituents independently selected from the group consisting of hydrocarbyl, silyl, tri (hydrocarbyl) silyl, tri (hydrocarbyl) germyl, halo, cyano, halohydrocarbyl, halocarbyl, N, N-di (hydrocarbyl ) amino, hydrocarbyloxy, and tri (hydrocarbyl) siloxy, said substituent having up to 20 atoms other than hydrogen, or optionally, two such substituents are optionally bonded together.
  • the A grouping is any divalent ligand group able to bond to two L groups.
  • Preferred bridging groups are those corresponding to the formula -(ER'' 2 ) X - or -(E'R'') X - as defined for Formula 1.
  • a most highly preferred A group is dimethylsilanediyl, dihydrocarbylamido borane or 1, 2-ethanediyl .
  • D' ligands include: ⁇ 4 -l, 4-diphenyl-l, 3- butadiene; ⁇ -1 , 3-pentadiene; ⁇ -1-phenyl-l, 3-pentadiene; ⁇ 4 -l,4- dibenzyl-1, 3-butadiene; ⁇ -2, 4-hexadiene; ⁇ -3-methyl-l, 3- pentadiene; ⁇ 4 -l, 4-ditolyl-l , 3-butadiene; and ⁇ 4 -l,4- bis (trimethylsilyl) -1, 3-butadiene .
  • terminally di-substituted derivatives that is, the 1,4- disubstituted 1, 3-butadienes are preferred.
  • a most preferred D' ligand is 1, 4-diphenyl-l, 3-butadiene .
  • Preferred Group 4 metal reagents include the well known tetrahalide, tetralkoxide, ⁇ -diketonate, and tetrakis (N, N- dialkyl ) amide salts, their Lewis base adducts, as well as mixed salts containing mixtures of halide, alkoxide, ⁇ -diketonate, and amide ligand groups.
  • the same result can be obtained by utilizing instead the corresponding salt in the +3 formal oxidation state, and using an oxidizing agent to increase the oxidation state of the metal at the same time, thereby generating the +4 oxidation state metal complex m situ, or reducing the starting +3 salt directly to the +2 oxidation state.
  • useful oxidizing agents include ferrocenium ion, Pb+2, Ag+1, and halohydrocarbons, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride or perchloroethylene .
  • the metal salts used as reactants of the formula M'X 2 D', M1X 4 or their corresponding Lewis base adducts are preferably Group 4 metal halide complexes. Highly preferred are compounds containing from 1 to 2, more preferably 2, Lewis base ligands. Preferred Lewis bases are ethers, amines, d ammes, triammes, phosphmes and thioethers, containing up to 30 atoms other than hydrogen.
  • trihydrocarbylammes and trihydrocarbylphosphmes containing from 1 to 20 carbons in each hydrocarbyl group, most preferably t ⁇ alkylphosphmes, and most highly preferably trimethylphosph e, t ⁇ ethylphosphme, tri-n- propylphosphme, t ⁇ isopropylphosphme or tri-n-butylphosphme .
  • the Lewis base provides desired stabilization to the metal complex intermediate, e. g., complexes of the formula, M'X 2 D'.
  • the resulting complexes of the formula (L-A- L)M'D' are relatively stable even in the absence of a Lewis base
  • the event the Lewis base is utilized to stabilize the intermediate complex, M'X 2 D' it is generally highly desirable in order not to affect the catalytic properties of the resulting metal complexes, to subsequently remove the Lewis base from the product, suitably by devolatilization or solubility difference, especially filtration or recrystallization.
  • the Lewis base is optionally recovered and recycled thereby reducing the cost of such component m the process.
  • Preferred intermediate complexes formed correspond to the formula: M'X 2 D' (L') 2 wherein M' is hafnium or zirconium, X is halide, D' is 1 , 4-diphenyl-l , 3-butadiene, and L' is t ⁇ methylphosphme, triethylphosph e, tri-n-propylphosphme, t ⁇ isopropylphosphme or tri-n-butylphosphme . More preferred intermediate metal complexes are those wherein X is chloride or bromide.
  • Most preferred intermediate complexes are zirconiumdichlo ⁇ de ( ⁇ -l, 4-diphenyl-l, 3-butadiene) bis (triethylphosphme) , and zirconiumdichlo ⁇ de ( ⁇ -l,4- d ⁇ phenyl-1, 3-butadiene) bis (t ⁇ -n-propylphosphme) .
  • the process involves combining the respective reactants, preferably in a solution, optionally while agitating, heating above ambient temperature (25°C) or a combination thereof. Recovery and purification of the intermediate products when a multiple step reaction is employed is optional and sometimes desirable, but is not required.
  • the process preferably is conducted in an inert, nonmterfermg solvent at a temperature from -100°C to 300°C, preferably from -78 to 130°C, most preferably from -40 to 120 C C.
  • Useful inert, nonmterfermg solvents for the formation of the complexes are aliphatic and aromatic hydrocarbons and halohydrocarbons, ethers, and cyclic ethers. Examples include straight and branched-cham hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, C ⁇ _ 4 dialkyl ethers, C ⁇ - dialkyl ether derivatives of (poly) alkylene glycols, and tetrahydrofuran. Mixtures of solvents from the foregoing list are also useful.
  • the recovery procedure involves separation of the resulting byproducts and devolatilization of the reaction medium. Extraction into a secondary solvent is optionally employed if desired. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation technique is optionally e employed.
  • the catalyst often contains as a byproduct a small quantity of the coupled diene, especially when starting from a trivalent or tetravalent metal starting material. However, the presence of this coupled diene does not interfere substantially with the activity of the catalyst, and it is not necessary to remove it.
  • the catalyst is optionally treated with an alkyl metal complex prior to the commencement of the hydrogenation reaction.
  • alkyl metal complexes include those represented by the structures R"'-Na, R"'-L ⁇ , R" 2 Mg,
  • the catalyst is advantageously treated with the alkyl metal complex at room temperature for a short period. This is optionally done m the presence of the polymer, copolymer or mixture to be hydrogenated, or prior to contacting with the polymer, copolymer or mixture to be hydrogenated.
  • the hydrogenating agent is introduced into the system prior to, during or after this step.
  • the polymer, copolymer, or mixture thereof to be hydrogenated m this process is characterized by having olefmic unsaturation either within the polymer chain, pendant to it, or both.
  • polymers or copolymers of one or more conjugated dienes such as butadiene, isoprene, 2,3- dimethylbutadiene, 2, 4-hexadiene, 1, 3-pentadiene, 2-methylpentad ⁇ ene and 1, 3-hexad ⁇ ene, or copolymers of one or more of the foregoing with one or more vinyl aromatic monomers .
  • copolymers of butadiene and isoprene, and especially polymers of butadiene are preferred on the basis of cost, availability, and beneficial properties.
  • the nature of the copolyme ⁇ zed vinyl aromatic monomer is generally not important, provided that any functional group which is optionally present is not substantially undesirably affected by and does not interfere substantially with the hydrogenation reaction.
  • copolymers of one or more conjugated dienes and a vinyl aromatic monomer such as styrene, ⁇ -methyl styrene, vinyl naphthalene, o-methyl styrene, p-methyl styrene, p-ethyl styrene, divinylbenzene .
  • styrene is most preferred.
  • the copolymer of the conjugated diene is optionally of any type, such as a random, block, tapered block, semi-block, or graft copolymer.
  • Block copolymers are preferred, particularly AB-type diblock or ABA-type triblock copolymers, wherein A represents a poly (vinyl aromatic) block and B represents a poly (diene) block.
  • A represents a poly (vinyl aromatic) block
  • B represents a poly (diene) block.
  • the poly (diene) portion constitutes 10 to 99, more preferably 25 to 85 percent of the total weight of the polymer.
  • Most preferred are block copolymers of butadiene and styrene of the AB or ABA type.
  • the most preferred polymer is a random or substantially random copolymer of butadiene and styrene.
  • the process of this invention is also applicable to the so-called living polymers or copolymers of conjugated dienes that contain terminal metal atoms .
  • These polymers or copolymers are optionally contacted with hydrogen to remove the terminal metal atoms.
  • This step is optionally done in conjunction with the hydrogenation of this invention. This is optionally achieved by contacting hydrogen, the catalyst and the metal-terminated polymer or copolymer in any order, thereby hydrogenating the polymer or copolymer and removing the terminal metal atom during or after the hydrogenation.
  • the molecular weight of the polymer or copolymer is not critical, and is mainly determined according to the properties required in the particular applications in which the hydrogenated polymer or copolymer will be used. However, since it is preferred to conduct the hydrogenation in the liquid phase, the polymer or copolymer is preferably molten or dissolved in some solvent in which the hydrogenation can be conducted. Thus, a number average molecular weight of from less than 1000 to 5,000,000 or more is useful. If the polymer or copolymer is cross-linked, it is preferably swellable in a solvent in which the hydrogenation can be conducted.
  • the practice of the invention advantageously facilitates hydrogenation while minimizing degradation or cleavage of the polymer backbone; therefore, it is preferred that the number average molecular weight is comparable before and after hydrogenation.
  • the number average molecular weight is comparable before and after hydrogenation.
  • Polymers or copolymers to be hydrogenated are optionally prepared by any process within the skill in the art, including anionic polymerization, radical polymerization, Zeigler-Natta polymerization, metallocene polymerization, or cationic polymerization in solution, bulk, mass, emulsion or gas phase processes or combinations thereof.
  • the hydrogenation is conducted by contacting the polymer or copolymer with a hydrogenating agent in the presence of the catalyst described before.
  • the hydrogenating agent can be any material that provides hydrogen to the reaction, but hydrogen gas is highly preferred because it is readily available, thus inexpensive, and easy to use.
  • hydrogen gas as the hydrogenating agent, the reaction is advantageously conducted by contacting the polymer or copolymer and catalyst with the hydrogen gas at an elevated pressure.
  • Useful hydrogen partial pressures are at least 20, preferably 100 psig (138, preferably 689 kPa gauge) and less than or equal to 5000, preferably 2000, more preferably 400 psig (34,474, preferably 13790, more preferably 2758 kPa gauge).
  • the hydrogenation reaction is optionally conducted at any temperature at which an adequate reaction rate is achieved.
  • a reaction time of greater than 72 hours is seldom commercially advantageous. Less than about 24 hours is usually preferred, with less than 6 hours more preferred.
  • an elevated temperature is used, since the reaction normally proceeds slowly at room temperature.
  • the use of the catalyst described herein allows for an acceptable reaction rate at mild to moderate temperatures.
  • a temperature in the range from 0 C C to 200°C is useful, and a preferred temperature range is from 25°C to 100°C, more preferably from 40°C to 75°C.
  • the amount of catalyst is chosen to provide an acceptable reaction rate.
  • catalyst 1 part by weight catalyst is used per 10 to 50,000, preferably 50 to 50,000 parts per weight of the polymer or copolymer. Higher amounts of catalyst tend to increase the reaction rate.
  • the hydrogenating agent is normally used in large stoichiometric excess, particularly if hydrogen is used.
  • th,e hydrogenation homogeneously with the polymer or copolymer in a liquid state. Accordingly, unless the polymer or copolymer is a liquid at room temperature or at a slightly elevated temperature (up to 75°C), it is preferred to conduct the hydrogenation in an inert solvent in which the catalyst is dissolved and the polymer or copolymer is dissolved or swollen. Any solvent which dissolves the polymer or copolymer and which does not engage in any undesirable side reactions with the reagents present in the hydrogenation reaction can be used.
  • Useful solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, ; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cycloheptane, ; and aromatic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, cumene, and benzene.
  • the solvent is ordinarily used in an amount sufficient to dissolve the polymer or copolymer, and to bring the viscosity of the resulting solution down to a workable range.
  • the resulting hydrogenated polymer or copolymer is often less soluble in the solvent than the starting polymer or copolymer.
  • an amount of solvent sufficient to dissolve the starting polymer or copolymer may not suffice to dissolve the hydrogenated polymer or copolymer product.
  • the precipitation of the insoluble product may facilitate isolation of the product by filtration.
  • the solvent is optionally used in an amount sufficient to dissolve the resulting hydrogenated polymer or copolymer.
  • the hydrogenating agent, polymer or copolymer and catalyst are contacted under conditions such that thorough contact of the hydrogenating agent with the polymer or copolymer is achieved.
  • this is readily achieved by adding hydrogen gas to a mixture of the polymer or copolymer and the catalyst with sufficient agitation to disperse hydrogen gas bubbles through the polymer or copolymer.
  • Contact times depend somewhat on the degree of hydrogenation desired; however, from 15 minutes to 24 hours, preferably 1 to 8 hours is ordinarily sufficient .
  • the hydrogenated polymer or copolymer is optionally and preferably recovered from the solvent, if any is used.
  • the hydrogenated polymer or copolymer is optionally caused to precipitate out of the solvent by the addition of a polar solvent, such as acetone or an alcohol, for example, methanol, ethanol or isopropanol.
  • a polar solvent such as acetone or an alcohol, for example, methanol, ethanol or isopropanol.
  • the solvent is optionally distilled off, or hot water or steam is optionally added and a water-solvent azeotrope distilled off.
  • the hydrogenated polymer or copolymer is optionally purified to remove residual catalyst or other impurities, but since the catalyst typically is used in small amounts, purification is optional.

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Abstract

L'invention concerne des composés organiques hydrogénés en présence de certains complexes métalliques du groupe IV bis(pentadiényl) contenant des ligands dioléfines π liés, conjugués, neutres. Ces complexes sont des catalyseurs d'hydrogénation efficaces pour les polymères présentant une insaturation éthylénique. Ils permettent également une hydrogénation sélective des sites d'insaturation éthylénique en présence de groupes aromatiques.
PCT/US2000/017163 1999-07-09 2000-06-22 Hydrogenation de polymeres insatures a l'aide de diolefine bivalente contenant des catalyseurs metalliques biscyclopentadienyl du groupe iv Ceased WO2001004164A2 (fr)

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JP2001509773A JP2003509520A (ja) 1999-07-09 2000-06-22 ２価のジエン含有ビスシクロペンタジエニルｉｖ族金属触媒を用いる不飽和ポリマーの水素化
MXPA02000311A MXPA02000311A (es) 1999-07-09 2000-06-22 Hidrogenacion de polimeros insaturados usando catalizador de bis-ciclopentadienilo - metal de grupo iv divalente que contienen dieno.
EP00941639A EP1257587B1 (fr) 1999-07-09 2000-06-22 Hydrogenation de polymeres insatures a l'aide de diolefine bivalente contenant des catalyseurs metalliques biscyclopentadienyl du groupe iv

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ES2223535T3 (es) 2005-03-01
WO2001004164A3 (fr) 2002-09-12
US6476283B1 (en) 2002-11-05

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